CN103183331B - The preparation method of Graphene - Google Patents
The preparation method of Graphene Download PDFInfo
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- CN103183331B CN103183331B CN201110447129.3A CN201110447129A CN103183331B CN 103183331 B CN103183331 B CN 103183331B CN 201110447129 A CN201110447129 A CN 201110447129A CN 103183331 B CN103183331 B CN 103183331B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 72
- 239000010439 graphite Substances 0.000 claims abstract description 72
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 238000009830 intercalation Methods 0.000 claims abstract description 21
- 230000002687 intercalation Effects 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 19
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 230000010355 oscillation Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 235000011194 food seasoning agent Nutrition 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- XQHAGELNRSUUGU-UHFFFAOYSA-M lithium chlorate Chemical group [Li+].[O-]Cl(=O)=O XQHAGELNRSUUGU-UHFFFAOYSA-M 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- -1 1,2-methylene diethyl ether Chemical compound 0.000 claims description 3
- 238000003487 electrochemical reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 claims description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 4
- 238000007614 solvation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000007571 dilatometry Methods 0.000 description 2
- 238000000407 epitaxy Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of preparation method of Graphene, comprise the following steps: provide electrolyte solution, this electrolyte solution is formed for electrolyte lithium salt being dissolved in organic solvent; Metallic lithium and graphite are provided, this metallic lithium and graphite are put into described electrolyte solution, this metallic lithium and graphite are contacted with each other in described electrolyte solution, thus make the lithium ion in electrolyte solution and organic solvent molecule jointly insert described graphite layers, to form graphite intercalation compound; And graphene film is separated from this graphite intercalation compound.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene.
Background technology
Graphene is that one passes through sp by carbon atom
2the honeycomb-like network structure that hydridization is formed, and be the two dimensional crystal material only having a carbon atom thickness.Cause investigator because Graphene has excellent electricity, optics, calorifics and mechanical property and study interest greatly.
2004, the people such as British scientist A.K.Geim and K.S.Novoselov, by the simplest " tear tape " method, successfully separated graphene film from highly oriented pyrolytic graphite.At present, the method preparing Graphene is the dilatometry of graphite oxide and reduction method, chemical Vapor deposition process and crystal epitaxy method etc. mainly.But although the dilatometry of described graphite oxide and reduction method can prepare a large amount of Graphenes with lower cost, but the electronic structure of Graphene and perfection of crystal are all subject to the destruction of strong oxidizer, make its performance be affected.Described chemical Vapor deposition process and crystal epitaxy method can prepare big area continuously and the graphene film of excellent performance, but the cost of these two kinds of methods is all higher.
Summary of the invention
In view of this, necessaryly provide a kind of cost lower and the electronic structure of Graphene and the graphene preparation method of perfection of crystal can not be destroyed.
A preparation method for Graphene, comprises the following steps: provide electrolyte solution, and this electrolyte solution is formed for electrolyte lithium salt being dissolved in organic solvent; Metallic lithium and graphite are provided, this metallic lithium and graphite are put into described electrolyte solution, this metallic lithium and graphite are contacted with each other in described electrolyte solution, thus make the lithium ion in electrolyte solution and organic solvent molecule jointly insert described graphite layers, to form graphite intercalation compound; And graphene film is separated from this graphite intercalation compound.
Compared to prior art, the preparation method of above-mentioned Graphene is simple, cost is lower, and in whole preparation process, do not add strong oxidizer, and by means of only reacting formation graphite intercalation compound between metallic lithium and graphite, avoid electronic structure and the perfection of crystal of destroying the final Graphene formed.
Accompanying drawing explanation
The graphene preparation method schema that Fig. 1 provides for the embodiment of the present invention.
Fig. 2 and Fig. 3 is the Graphene stereoscan photograph adopting preparation method of the present invention to prepare.
Embodiment
Below with reference to accompanying drawing, the graphene preparation method that the embodiment of the present invention provides is described in further detail.
Refer to Fig. 1, the embodiment of the present invention provides a kind of preparation method of Graphene, and the method comprises the following steps:
Step one, provides electrolyte solution, and this electrolyte solution is formed for electrolyte lithium salt being dissolved in organic solvent;
Step 2, metallic lithium and graphite are provided, this metallic lithium and graphite are put into described electrolyte solution, this metallic lithium and graphite are contacted with each other in described electrolyte solution, thus make the molecule of the lithium ion in electrolyte solution and organic solvent jointly insert described graphite layers, to generate a graphite intercalation compound; And
Step 3, separates graphene film from this graphite intercalation compound.
Below will be described in detail above steps.
In described step one, this electrolyte solution is formed for electrolyte lithium salt being dissolved in organic solvent, and described electrolyte lithium salt dissociates lithium ion in described organic solvent.This electrolyte solution can be conventional lithium ion battery electrolyte solution.Described electrolyte lithium salt for may be dissolved in described organic solvent, and dissociation can go out the lithium salts of lithium ion in this organic solvent.This lithium salts can be in lithium chlorate, lithium nitrate, lithium chloride, lithium acetate, lithium hexafluoro phosphate, di-oxalate lithium borate, LiBF4 and trifluoromethyl sulfonic acid lithium one or more.
The organic solvent of described electrolyte solution is lithium salts described in solubilized and the remarkable solvent reacted does not occur with metallic lithium.This organic solvent can be enumerated as, but be not limited to propylene carbonate (PC), tetrahydrofuran (THF) (THF), 1,2-glycol dimethyl ether (DME), 1,2-diethoxyethane (DEE), 1,2-dibutoxy ethane (DBE), 1,2-Methylal(dimethoxymethane) (DMM) and 1,2-methylene diethyl ether (DEM) one or more.
The amount of described organic solvent is not limit, and only needs can dissolve described lithium salts completely, and the metallic lithium in step 2 and graphite can be immersed in described electrolyte solution completely.
In addition, the volumetric molar concentration of described electrolyte lithium salt in electrolyte solution is not limit, and such as, the volumetric molar concentration of this electrolyte lithium salt can be less than or equal to the saturation concentration of this electrolyte lithium salt in described organic solvent, be preferably, the volumetric molar concentration of this electrolyte lithium salt is 0.05mol/L ~ 20mol/L.
Described metallic lithium can be Powdered, sheet, fragmental or bulk.Described graphite can be electrographite, natural flake graphite, high temperature pyrolysis graphite or expansible black lead etc.Be preferably natural flake graphite.Described graphite can be powder shaped or particulate state.Be specially, the particle diameter of this graphite can be 0.05 micron ~ 1000 microns.The more little contact area that more can increase between this metallic lithium and described graphite of grain diameter of this powdery metal lithium or reguline metal lithium.
Graphite has good laminate structure, and the crystal face interlamellar spacing of graphite is roughly 0.1335 nanometer.In described electrolyte solution, lithium ion is combined with solvent molecule by ionic solvation (ionicsolvation), forms solvation lithium ion.In described step 2, under the effect of described electrolyte solution, described metallic lithium and described graphite form potential difference by contacting with each other, thus cause electrochemical reaction.Through this electrochemical reaction, described metallic lithium also forms lithium ion and is dissolved in described electrolyte solution, and and then also form solvation lithium ion, and this solvation lithium ion inserts graphite layers, forms graphite intercalation compound.The crystal face interlamellar spacing of this graphite intercalation compound due to lithium ion and solvent molecule common insertion and increase, namely the crystal face interlamellar spacing of graphite self is obviously greater than, thus graphite bonding force is between layers weakened, described graphite linings is easily peeled off, forms Graphene.In the process of this formation graphite layers and thing, described graphite is without the need to the oxidation through strong oxidizer.
Further, fully contact to make described metallic lithium and graphite for making described metallic lithium and graphite Homogeneous phase mixing in described electrolyte solution, the electrolyte solution of metallic lithium and graphite is put into described in can stirring further in step 2, the mode of this stirring is not limit, and can be mechanical stirring, magnetic agitation or ultrasonic disperse.
Further, in step 2, for accelerating the speed of described reaction, described in can heating, put into the electrolyte solution of metallic lithium and graphite.The mode of this heating can be normal heating or hyperbaric heating.When hyperbaric heating, the described electrolyte solution putting into metallic lithium and graphite can be placed in a seal-off pressure reactor and be heated to a preset temperature, and constant temperature one scheduled time, this preset temperature can be 150oC ~ 300oC, and constant temperature time is 30 minutes ~ 40 hours.
In described step 3, because the interlamellar spacing between above-mentioned graphite intercalation compound is comparatively large compared to the interlamellar spacing of former graphite, therefore, the graphene layer in this graphite intercalation compound is very easily stripped.From graphite intercalation compound, the mode that graphene layer strips down should not limit, ultrasonic disperse, ball milling or magnetic agitation etc. can be adopted.In the present embodiment, the method for this stripping is by graphite intercalation compound sonic oscillation in a liquid phase medium.Liquid phase medium is herein wider than above-mentioned organic solvent range of choice, can be above-mentioned organic solvent, also can be water or conventional lower molecular weight organic solvent, as ethanol, ether and acetone.Through sonic oscillation, layer and the layer of graphite intercalation compound are stripped out, thus are formed in liquid phase medium and suspend and the Graphene disperseed.The ultrasonic power of described sonic oscillation can be more than or equal to 100W, and ultrasonic time can be 5 minutes to 400 minutes.
In addition, for extracting described Graphene, after described sonic oscillation, further Graphene can be filtered, washing and drying.Such as, the method by centrifugal separation or suction filtration removes residual lithium salts, metallic lithium and solvent etc.After described residue to be removed, can dry described Graphene, be specially, by dry described Graphenes of mode such as lyophilize, supercritical fluid drying, seasoning or heat oven dry, thus acquisition can direct applied Graphene.
The preparation method of above-mentioned Graphene is simple, with low cost, easily realize the suitability for industrialized production of Graphene, and whole preparation process is gentle, does not add strong oxidizer, can not destroy electronic structure and the perfection of crystal of the final Graphene formed.
Embodiment 1
Be dissolved in propylene carbonate by lithium chlorate and form electrolyte solution, the volumetric molar concentration of this lithium chlorate is 1.5mol/L.Be that the natural flake graphite of 1 micron and powdery metal lithium and electrolyte solution are mixed to form a mixed solution by grain diameter, and in autoclave, at the temperature of 190oC, heat described mixed solution react to make described metallic lithium and described graphite for 1 hour, form graphite intercalation compound.Graphite intercalation compound described in sonic oscillation, thus form graphene suspension, the power of described sonic oscillation is 1500W, and ultrasonic time is 40 minutes.Adopt centrifugal separation to be extracted by the Graphene in described suspension, adopt the mode of seasoning dry the Graphene extracted afterwards.Refer to the stereoscan photograph that Fig. 2 and Fig. 3 is the Graphene that the present embodiment prepares.
Embodiment 2
Be dissolved in tetrahydrofuran (THF) by lithium chloride and form electrolyte solution, this lithium chloride volumetric molar concentration is 0.5mol/L.Be that the natural flake graphite of 8 microns and powdery metal lithium and described electrolyte solution are mixed to form a mixed solution by grain diameter, and at the temperature of 200oC, heat described mixed solution in high pressure water heating kettle can react to make described metallic lithium and described graphite for 1.5 hours, form graphite intercalation compound.Through there is the mixed solution of redox reaction described in sonic oscillation, thus form graphene suspension, the power of described sonic oscillation is 600W, and ultrasonic time is 120 minutes.Adopt centrifugal separation to be extracted by the Graphene in described suspension, adopt the mode of seasoning dry the Graphene extracted afterwards.
Embodiment 3
Be dissolved in by lithium nitrate in 1,2-glycol dimethyl ether and form electrolyte solution, the volumetric molar concentration of this lithium nitrate is 2mol/L.Be that the natural flake graphite of 50 microns and powdery metal lithium and described electrolyte solution are mixed to form a mixed solution by grain diameter, and at the temperature of 300oC, heat described mixed solution 10 hours to react formation graphite intercalation compound to make described metallic lithium and described graphite.Mixed solution through reacting described in sonic oscillation, thus form graphene suspension, the power of described sonic oscillation is 250W, and ultrasonic time is 30 minutes.Adopt centrifugal separation to be extracted by the Graphene in described suspension, adopt the mode of seasoning dry the Graphene extracted afterwards.
In addition, those skilled in the art also can do other changes in spirit of the present invention, and certainly, these changes done according to the present invention's spirit, all should be included within the present invention's scope required for protection.
Claims (12)
1. a preparation method for Graphene, comprises the following steps:
There is provided electrolyte solution, this electrolyte solution is formed for electrolyte lithium salt being dissolved in organic solvent;
Metallic lithium and graphite are provided, this metallic lithium and graphite are put into described electrolyte solution, this metallic lithium and graphite is made to contact with each other in described electrolyte solution and form potential difference and cause electrochemical reaction, thus make the lithium ion in electrolyte solution and organic solvent molecule jointly insert described graphite layers, to form graphite intercalation compound; And
Graphene film is separated from this graphite intercalation compound.
2. the preparation method of Graphene as claimed in claim 1, it is characterized in that, described electrolyte lithium salt is lithium chlorate, lithium nitrate, lithium chloride, lithium hexafluoro phosphate, LiBF4 or trifluoromethyl sulfonic acid lithium.
3. the preparation method of Graphene as claimed in claim 1, it is characterized in that, described organic solvent can dissolve described lithium salts.
4. the preparation method of Graphene as claimed in claim 3, it is characterized in that, described organic solvent is propylene carbonate, tetrahydrofuran (THF), 1,2-glycol dimethyl ether, 1,2-diethoxyethane, 1,2-dibutoxy ethane, 1,2-Methylal(dimethoxymethane) or 1,2-methylene diethyl ether.
5. the preparation method of Graphene as claimed in claim 1, it is characterized in that, the volumetric molar concentration of described electrolyte lithium salt in described electrolyte solution is 0.1mol/L ~ 100mol/L.
6. the preparation method of Graphene as claimed in claim 1, it is characterized in that, described graphite is electrographite, natural flake graphite or expansible black lead.
7. the preparation method of Graphene as claimed in claim 1, is characterized in that, after this metallic lithium and graphite are put into described electrolyte solution, heat described solution further in water heating kettle.
8. the preparation method of Graphene as claimed in claim 7, it is characterized in that, described Heating temperature is 150 DEG C ~ 300 DEG C, and heat-up time is 30 minutes ~ 40 hours.
9. the preparation method of Graphene as claimed in claim 1, it is characterized in that, the described mode separating graphene film from this graphite intercalation compound is sonic oscillation.
10. the preparation method of Graphene as claimed in claim 9, it is characterized in that, the power of described ultrasonic disperse is for being more than or equal to 100W, and ultrasonic time is 5 minutes to 400 minutes.
The preparation method of 11. Graphenes as claimed in claim 1, is characterized in that, after separating graphene film, adopts centrifugal separation or suction method to extract Graphene.
The preparation method of 12. Graphenes as claimed in claim 11, is characterized in that, further dry described graphene film, and this drying mode is lyophilize, supercritical fluid drying, seasoning or heat oven dry.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110447129.3A CN103183331B (en) | 2011-12-28 | 2011-12-28 | The preparation method of Graphene |
| TW100150071A TWI448425B (en) | 2011-12-28 | 2011-12-30 | Method for making graphene |
| US13/554,127 US9017639B2 (en) | 2011-12-28 | 2012-07-20 | Method for making graphene |
| JP2012207967A JP5668035B2 (en) | 2011-12-28 | 2012-09-21 | Method for producing graphene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110447129.3A CN103183331B (en) | 2011-12-28 | 2011-12-28 | The preparation method of Graphene |
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| CN103183331A CN103183331A (en) | 2013-07-03 |
| CN103183331B true CN103183331B (en) | 2016-01-20 |
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| US (1) | US9017639B2 (en) |
| JP (1) | JP5668035B2 (en) |
| CN (1) | CN103183331B (en) |
| TW (1) | TWI448425B (en) |
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| KR101563585B1 (en) * | 2014-03-31 | 2015-10-28 | 한국과학기술연구원 | Method for preparation of graphene using spontaneous process |
| CN105088261B (en) * | 2014-05-14 | 2017-10-20 | 国能纳米科技有限公司 | The preparation method of graphene |
| CN104058395A (en) * | 2014-07-11 | 2014-09-24 | 武汉理工大学 | Method for preparing graphene by carrying out ultrasonic treatment on lithium intercalated graphite |
| CN104264179B (en) * | 2014-09-17 | 2016-06-22 | 中国科学院山西煤炭化学研究所 | A kind of method being prepared Graphene by graphite raw ore electrolysis |
| CN104264178B (en) * | 2014-09-17 | 2016-11-30 | 中国科学院青海盐湖研究所 | A kind of electrocatalytic oxidation prepares the method for graphene oxide |
| CN104240964B (en) * | 2014-09-18 | 2017-02-15 | 上海交通大学 | Method for achieving in situ composition of graphene and activated carbon through supercutical fluid |
| CN104860311B (en) * | 2015-05-26 | 2017-01-25 | 广东烛光新能源科技有限公司 | Preparation method of graphene |
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